CN111154061A - Silicon-containing polyurethane resin and preparation method and application thereof - Google Patents
Silicon-containing polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN111154061A CN111154061A CN202010104254.3A CN202010104254A CN111154061A CN 111154061 A CN111154061 A CN 111154061A CN 202010104254 A CN202010104254 A CN 202010104254A CN 111154061 A CN111154061 A CN 111154061A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D06N2211/00—Specially adapted uses
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Abstract
The invention discloses a silicon-containing polyurethane resin and a preparation method and application thereof, wherein the silicon-containing polyurethane resin is prepared by adopting the following components in parts by mass as starting raw materials: 100 portions of oligomer dihydric alcohol, 0.5 to 20 portions of dihydric alcohol chain extender, 0.1 to 5 portions of silicon-containing chain extender, 6 to 150 portions of diisocyanate, 0.1 to 2 portions of antioxidant, 0.5 to 2 portions of silicon-containing terminator and 700 portions of solvent 600-. The silicon-containing polyurethane resin prepared by the invention improves the antifouling property of the material, and simultaneously has better performances such as wear resistance, scratch resistance and the like than the silicon-free polyurethane with the same structure. The synthetic leather coating prepared by the silicon-containing polyurethane resin has good antifouling property, wear resistance, scraping resistance and stable pigment dispersing property.
Description
Technical Field
The invention relates to a silicon-containing polyurethane resin and application of a polyurethane synthetic leather coating, belonging to the fields of polyurethane resin materials and polyurethane synthetic leather.
Background
The polyurethane resin has excellent wear resistance, scratch resistance and the like, is widely applied to the fields of coatings and synthetic leather, and is one of the most commonly used resins in coatings of the coatings and the synthetic leather at present. However, when polyurethane is used as a synthetic leather coating, the antifouling performance of the coating is poor, and the antifouling treatment method which is commonly used at present is to spray, roll or print a layer of antifouling treatment agent consisting of a low-surface-tension material on the surface of the coating so as to prevent the adhesion of fouling substances on the surface of the coating, thereby achieving the antifouling effect. Two major problems arise with this approach: (1) the adhesion fastness of the treating agent coating is low, and the treating layer is easy to fall off; (2) the antifouling treatment agent itself has low wear resistance and aging resistance.
The surface tension of the polyurethane coating can be effectively reduced by adding a certain amount of silicon structures into the polyurethane resin, so that the antifouling effect is achieved. Patent CN 105339405 a discloses a polyurethane with a siloxane structural unit as a soft segment, wherein the polyurethane has a far lower wear resistance than that of polyurethane without siloxane because the soft segment is composed of siloxane structure, and the linear siloxane structure is not favorable for stable dispersion of pigment in the resin, and is not suitable for application in the field of preparation of polyurethane synthetic leather coatings. Patent CN 109517131 a discloses a thermoplastic silicone polyurethane containing 2-40%, preferably 4-20% of macromolecular organic silicon containing active hydrogen in soft segment and its preparation method, and the silicone polyurethane also contains more linear organic silicon structural units on the soft segment, so that the problems of obvious decrease of wear resistance, difficult stable dispersion of pigment, etc. exist, and thus it can not be applied to the preparation of polyurethane synthetic leather coating.
Disclosure of Invention
The invention aims to provide a silicon-containing polyurethane resin, a preparation method thereof and application thereof in a polyurethane synthetic leather coating, so as to overcome the defects of the existing product.
The silicon-containing polyurethane resin provided by the invention is prepared from the following components in parts by mass as starting raw materials:
oligomer diol 100-300 parts
0.5-20 parts of glycol chain extender
0.1-5 parts of silicon-containing chain extender
6-150 parts of diisocyanate
0.1 to 2 portions of antioxidant
0.5-2 parts of silicon-containing terminator
Solvent 600-700 parts
The oligomer diol is one or more of polyether diol or polyester diol with the number average molecular weight of 1000-3000.
The polyether diol is one or more selected from polyoxypropylene diol (PPG) with the number average molecular weight of 1000-3000, polytetrahydrofuran diol (PTMEG) and polyoxyethylene diol (PEG).
The polyester diol is one or more of adipic acid polyester diol, polycaprolactone diol and polycarbonate diol with the number average molecular weight of 1000-3000.
The dihydric alcohol chain extender is one or more selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
The silicon-containing chain extender is selected from one or more of silicon glycol, silane containing dihydroxyl hydrocarbon group, silane containing dimercapto hydrocarbon group and silane containing diamino hydrocarbon group;
the silicon diol is selected from one or more of diphenyl silicon diol, dipropylene silicon diol, 1, 4-bis (dimethyl hydroxyl silicon-based) benzene and dimethyl silane diol;
the silane containing the dihydroxyalkyl is selected from one or more of the group consisting of silane, silane;
the silane containing dimercaptohydrocarbyl is selected from one or more of silane, silane;
the silane containing the bisaminohydrocarbyl is selected from one or more of silane, silane and silane. .
The diisocyanate is selected from one or more of diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Naphthalene Diisocyanate (NDI) and p-phenylene diisocyanate (PPDI).
The antioxidant is selected from one or more of antioxidant 1790, antioxidant 168, octylated diphenylamine and butylated diphenylamine.
The silicon-containing terminator is selected from one or more of monohydroxy silanol, monohydroxy hydrocarbyl silane, monothiohydroxy hydrocarbyl-containing silane and monoamino hydrocarbyl-containing silane;
the monohydroxy silanol is trimethyl silanol, triethyl silanol and tert-butyl dimethyl silanol;
the monohydroxy hydrocarbyl silane is selected from one or more of silane, silane and silane;
the silane containing the single mercapto-hydrocarbyl is selected from one or more of silane, silane and silane;
the silane containing the monoamino hydrocarbon group is selected from one or more of silane, silane and silane.
The solvent is selected from one or more of toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethylacetamide, and the preferable solvent is selected from one or more of ethyl acetate, butyl acetate, acetone, methyl ethyl ketone and dimethyl sulfoxide.
The preparation method of the silicon-containing polyurethane resin comprises the following steps:
(1) putting oligomer dihydric alcohol, a dihydric alcohol chain extender, a silicon-containing chain extender, an antioxidant and 30% of solvent into a reactor, and uniformly stirring at 40-60 ℃;
(2) then raising the temperature to 70-100 ℃, then adding diisocyanate and the rest solvent in batches to react until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding a silicon-containing terminator to react for 0.5-1 hour, and obtaining the silicon-containing polyurethane resin.
The silicon-containing polyurethane resin can be used for preparing polyurethane coating synthetic leather with good antifouling property.
The preparation method of the polyurethane coating synthetic leather with good antifouling property comprises the following steps:
(1) stirring and mixing the silicon-containing polyurethane resin, the solvent and the pigment to prepare slurry, coating the slurry on release paper, wherein the coating thickness is 100-300 microns, and drying at the temperature of 80-150 ℃ to obtain a polyurethane coating with good antifouling performance;
(2) and (2) coating an adhesive layer on the polyurethane coating obtained in the step (1), wherein the coating thickness is 50-200 microns, adhering the polyurethane coating to base cloth, drying at the temperature of 100-150 ℃, and stripping release paper to obtain the antifouling polyurethane synthetic leather.
The release paper is a carrier material, has the function of endowing patterns on a synthetic leather coating, is a well-known material, and can be referred to in the literature, synthetic leather materials and technology (Qujiabo, etc.. synthetic leather materials and technology [ M ]. Beijing: chemical industry publishers, 2015.);
the adhesive layer is a coating formed by bonding a coating film and base cloth together by adopting a polyurethane adhesive;
the polyurethane adhesive is one of liquid polyurethane resin or two-liquid polyurethane resin;
the base cloth is one of non-woven fabric, woven fabric or superfine fiber synthetic leather base cloth.
Compared with the prior art, the invention has the following beneficial effects
(1) According to the invention, the silicon-containing micromolecule dihydric alcohol or the silicon-containing micromolecule diamine is used as the chain extender, and the silicon-containing structure is introduced into the hard segment, so that the surface tension of the material is reduced, the antifouling property of the material is improved, and the adverse effect that the pigment is difficult to stably disperse due to the introduction of the macromolecular silicon structure into the soft segment in the prior art is overcome.
(2) According to the invention, a small amount of silicon-containing structures are introduced into the molecular chain of the polyurethane resin, so that the antifouling performance of the material is improved, and the performances of wear resistance, scratch resistance and the like of the material are better than those of silicon-free polyurethane with the same structure.
(3) The silicon-containing polyurethane resin does not need to be added with a catalyst in the preparation process, and the adverse effect of the toxicity of the catalyst on the health of operators is eliminated.
(4) The synthetic leather coating prepared by the silicon-containing polyurethane resin has good antifouling property, wear resistance, scratch resistance and stable pigment dispersion property, and does not have the risk of organic silicon migrating to the surface of the coating. The preparation of the coating is the same as that of the conventional polyurethane synthetic leather, a special preparation process is not required to be added, and equipment investment is saved. Compared with the conventional polyurethane coating with the antifouling effect, the coating does not need post-treatment processes such as spraying, printing or rolling coating, and the like, thereby simplifying the production process.
Detailed Description
The present invention is described in further detail below by way of examples, but is not limited thereto.
Polyurethane binder in examples: JF-A-WV2010 (bonding layer polyurethane resin publicly sold by Zhejiang Huafeng synthetic resin Co., Ltd.).
The silane containing a bishydroxyhydrocarbon group (e.g., silane containing a dimercaptohydrocarbon group (e.g., silane) containing a dimercaptohydrocarbon group, silane containing a bisaminohydrocarbon group (e.g., silane) containing a monohydroxyhydrocarbon group, silane containing a monosulfydroxyhydrocarbon group (e.g., silane) containing a monoaminohydrocarbon group (e.g., silane) in the examples are conventional organosilicon substances, and the synthesis processes and applications of these substances are disclosed in "organosilicon product synthesis process and applications" (second edition) (Yuguo bridge et al. organosilicon product synthesis process and applications [ M ]. Beijing: chemical industry Press, 2010.).
The base fabric in the examples was: the polyurethane superfine fiber synthetic leather base cloth is black and 1.2 mm thick, can be purchased from the market, and can also be prepared by a method disclosed in the literature synthetic leather materials and technology (Qujiabo, et al. synthetic leather materials and technology [ M ]. Beijing: chemical industry publishers, 2015.).
Example 1
| Kind of raw material | Substance(s) | Parts by mass | Remarks for note |
| Oligomer diols | Polyoxypropylene diol (trade name: Voranol 220- | 300 | Number average molecular weight 1200, product of Dow |
| Dihydric alcohol chain extender | Ethylene glycol | 20 | |
| Silicon-containing chain extender | 5 | ||
| Antioxidant agent | Antioxidant 1790 | 2 | |
| 30% of solvent | Dimethyl formamide | 210 | |
| Diisocyanate | Diphenylmethane diisocyanate | 150 | |
| 70% of solvent | Dimethyl formamide | 490 | |
| Silicon-containing terminating agent | 2 |
The preparation process of the silicon-containing polyurethane resin comprises the following steps:
(1) 300 parts of polyoxypropylene glycol, 20 parts of ethylene glycol, 5 parts of antioxidant 1790 in 2 parts and 210 parts of dimethylformamide are added to a reactor and stirred uniformly at a temperature of 60 ℃.
(2) And raising the temperature to 100 ℃, adding 150 parts of diphenylmethane diisocyanate into the reactor in batches, diluting the mixture in batches by using the residual solvent, reacting the mixture until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding 2 parts of the mixture, and reacting for 1 hour to obtain the silicon-containing polyurethane resin.
Comparative example 1
The silicon-containing chain extender in example 1 was replaced with the same molar fraction of ethylene glycol; the silicon-containing terminator is replaced by methanol with the same molar fraction, and the polyurethane resin is obtained by adopting the same preparation process.
Example 2
The preparation process of the silicon-containing polyurethane resin comprises the following steps:
(1) 100 parts of polytetrahydrofuran diol, 0.5 part of 1, 5-pentanediol, 0.1 part of diphenyl silanediol, 0.1 part of antioxidant 168 and 180 parts of dimethyl sulfoxide are added into a reactor and stirred uniformly at the temperature of 50 ℃.
(2) And raising the temperature to 90 ℃, adding 6 parts of p-phenylene diisocyanate into the reactor in batches, diluting the p-phenylene diisocyanate with the rest solvent in batches, reacting until the viscosity is 70-130 pas/25 ℃, then cooling to below 60 ℃, adding 0.5 part of trimethylsilanol, and reacting for 1 hour to obtain the silicon-containing polyurethane resin.
Comparative example 2
The silicon-containing chain extender in example 2 is replaced by the same mole fraction of 1, 5-pentanediol; the silicon-containing terminator is replaced by methanol with the same molar fraction, and the polyurethane resin is obtained by adopting the same preparation process.
Example 3
The preparation process of the silicon-containing polyurethane resin comprises the following steps:
(1) 200 parts of polyoxyethylene glycol, 7.6 parts of 1, 3-propanediol, 1.18 parts of octylated diphenylamine and 195 parts of dimethylacetamide are charged into a reactor and stirred uniformly at a temperature of 40 ℃.
(2) And raising the temperature to 70 ℃, adding 45.15 parts of naphthalene diisocyanate into the reactor in batches, diluting the mixture in batches by using the rest solvent, reacting the mixture until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding 1.03 parts of the mixture, and reacting for 0.5 hour to obtain the silicon-containing polyurethane resin.
Comparative example 3
The silicon-containing chain extender in example 3 is replaced by the same molar part of 1, 3-propanediol; the silicon-containing terminator is replaced by methanol with the same molar fraction, and the polyurethane resin is obtained by adopting the same preparation process.
Example 4
The preparation process of the silicon-containing polyurethane resin comprises the following steps:
(1) 250 parts of adipic acid-based polyester diol, 18 parts of 1, 4-butanediol, 3.52 parts of butylated diphenylamine, 1.8 parts of dimethylformamide and 204 parts of dimethylformamide are charged into a reactor and stirred uniformly at a temperature of 45 ℃.
(2) And raising the temperature to 80 ℃, adding 82 parts of toluene diisocyanate into the reactor in batches, diluting the mixture in batches by using the residual solvent, reacting the mixture until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding 0.6 part of toluene diisocyanate, and reacting for 0.6 hour to obtain the silicon-containing polyurethane resin.
Comparative example 4
The silicon-containing chain extender in example 4 is replaced by the same molar part of 1, 4-butanediol; the silicon-containing terminator is replaced by methanol with the same molar fraction, and the polyurethane resin is obtained by adopting the same preparation process.
Example 5
The preparation process of the silicon-containing polyurethane resin comprises the following steps:
(1) 160 parts of polycaprolactone diol, 11.8 parts of 1, 6-hexanediol, 1.18 parts of antioxidant 1790 and 204 parts of dimethylacetamide are added into a reactor and stirred uniformly at the temperature of 50 ℃.
(2) And raising the temperature to 90 ℃, adding 50 parts of diphenylmethane diisocyanate into the reactor in batches, diluting the mixture in batches by using the residual solvent, reacting the mixture until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding 1.8 parts of the mixture, and reacting for 0.7 hour to obtain the silicon-containing polyurethane resin.
Comparative example 5
The silicon-containing chain extender in example 5 was replaced with the same mole fraction of 1, 6-hexanediol; the silicon-containing terminator is replaced by methanol with the same molar fraction, and the polyurethane resin is obtained by adopting the same preparation process.
Example 6
The preparation process of the silicon-containing polyurethane resin comprises the following steps:
(1) 120 parts of polycarbonate diol, 1.8 parts of 1, 3-butanediol, 3.54 parts of antioxidant 168 and 200 parts of dimethyl sulfoxide are added into a reactor and stirred uniformly at the temperature of 55 ℃.
(2) And raising the temperature to 95 ℃, adding 28 parts of diphenylmethane diisocyanate into the reactor in batches, diluting the mixture in batches by using the residual solvent, reacting the mixture until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding 1.8 parts of the mixture, and reacting for 0.8 hour to obtain the silicon-containing polyurethane resin.
Comparative example 6
The silicon-containing chain extender in example 6 was replaced with the same mole fraction of 1, 3-butanediol; the silicon-containing terminator is replaced by methanol with the same molar fraction, and the polyurethane resin is obtained by adopting the same preparation process.
Example 7
Mixing the polyurethane resins prepared in the above examples 1 to 6 and comparative examples 1 to 6 with a solvent and a pigment respectively to prepare slurry, coating the slurry on release paper with a coating thickness of 200-micron, and drying at 120 ℃ to obtain a polyurethane coating; and then coating an adhesive layer on the polyurethane coating, wherein the coating thickness is 100 microns, adhering the polyurethane coating on the synthetic leather base cloth, drying at 140 ℃, and stripping release paper to obtain the polyurethane synthetic leather.
The prepared polyurethane synthetic leather is subjected to an antifouling test according to PV3968 (the judgment grade is from grade 1 to grade 5, wherein grade 1 is the worst, and grade 5 is the best), a wear resistance test is performed according to SAE J948 (the model of a grinding wheel is CS-10, the load is 1000g, the wear resistance of the coating is judged by testing the revolution of the worn coating), a scratch resistance test is performed according to SAE J365-2012 (an A-type scraping head is 900g, and the scratch resistance is judged by testing the revolution of the scraped coating), and the test results are as follows:
according to the results of the antifouling, wear-resisting and scratch-resisting tests of the synthetic leather prepared from the polyurethane resin in the above examples and comparative examples, it can be known that the antifouling property, wear-resisting property and scratch-resisting property of the polyurethane resin can be remarkably improved by adding a certain amount of silicon-containing component into the chain extender and the terminator.
Claims (11)
1. The silicon-containing polyurethane resin is characterized by comprising the following components in parts by mass as initial raw materials:
oligomer diol 100-300 parts
0.5-20 parts of glycol chain extender
0.1-5 parts of silicon-containing chain extender
6-150 parts of diisocyanate
0.1 to 2 portions of antioxidant
0.5-2 parts of silicon-containing terminator
Solvent 600-700 parts.
2. The silicone-containing polyurethane resin as claimed in claim 1, wherein the oligomer diol is one or more of polyether diol or polyester diol having a number average molecular weight of 1000-3000;
the polyether diol is selected from one or more of polyoxypropylene diol, polytetrahydrofuran diol and polyoxyethylene diol with the number average molecular weight of 1000-3000;
the polyester diol is selected from one or more of adipic acid polyester diol, polycaprolactone diol and polycarbonate diol with the number average molecular weight of 1000-3000.
3. The silicon-containing polyurethane resin of claim 1, wherein the diol chain extender is one or more selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol;
the silicon-containing chain extender is selected from one or more of silicon glycol, silane containing dihydroxyl hydrocarbon group, silane containing dimercapto hydrocarbon group and silane containing diamino hydrocarbon group.
4. The silicon-containing polyurethane resin according to claim 3, wherein the silicon diol is one or more selected from diphenyl silicon diol, dipropylene silicon diol, 1, 4-bis (dimethylhydroxysilyl) benzene, and dimethylsilanediol;
the silane containing the dihydroxyalkyl is selected from one or more of the group consisting of silane, silane;
the silane containing dimercaptohydrocarbyl is selected from one or more of silane, silane;
the silane containing the bisaminohydrocarbyl is selected from one or more of silane, silane and silane.
5. The silicon-containing polyurethane resin of claim 1, wherein the silicon-containing terminator is one or more selected from the group consisting of monohydroxysilols, monohydroxyhydrocarbyl silanes, monothiocarbyl-containing silanes, and monoaminohydrocarbyl-containing silanes.
6. The silicone-containing polyurethane resin of claim 5, wherein the monohydroxysilicitol is selected from one or more of trimethylsilanol, triethylsilanol, and t-butyldimethylsilanol;
the monohydroxy hydrocarbyl silane is one or more of silane, silane and silane;
the silane containing the single mercapto-hydrocarbyl group is one or more of silane, silane and silane;
the silane containing monoaminohydrocarbyl is one or more of silane, silane and silane.
7. The silicon-containing polyurethane resin according to claim 1, wherein the diisocyanate is one or more selected from the group consisting of diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, and p-phenylene diisocyanate;
the antioxidant is selected from one or more of antioxidant 1790, antioxidant 168, octylated diphenylamine and butylated diphenylamine;
the solvent is one or more of toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide and dimethylacetamide.
8. The method of preparing a silicon-containing polyurethane resin according to any one of claims 1 to 7, comprising the steps of:
(1) putting oligomer dihydric alcohol, a dihydric alcohol chain extender, a silicon-containing chain extender, an antioxidant and 30% of solvent into a reactor, and uniformly stirring at 40-60 ℃;
(2) then raising the temperature to 70-100 ℃, then adding diisocyanate and the rest solvent in batches to react until the viscosity is 70-130 Pa.s/25 ℃, then cooling to below 60 ℃, adding a silicon-containing terminator to react for 0.5-1 hour, and obtaining the silicon-containing polyurethane resin.
9. Use of the silicon-containing polyurethane resin according to any one of claims 1 to 7 for preparing polyurethane coated synthetic leather having good antifouling properties.
10. Use of a silicon-containing polyurethane resin according to claim 9, wherein the method of application comprises the steps of:
(1) stirring and mixing the silicon-containing polyurethane resin, the solvent and the pigment to prepare slurry, coating the slurry on release paper, wherein the coating thickness is 100-300 microns, and drying at the temperature of 80-150 ℃ to obtain a polyurethane coating with good antifouling performance;
(2) and (2) coating an adhesive layer on the polyurethane coating obtained in the step (1), wherein the coating thickness is 50-200 microns, adhering the polyurethane coating to base cloth, drying at the temperature of 100-150 ℃, and stripping release paper to obtain the antifouling polyurethane synthetic leather.
11. The use of the silicone-containing polyurethane resin of claim 10, wherein in the method of use, the release paper is a carrier material;
the adhesive layer is a coating formed by bonding a coating film and base cloth together by adopting a polyurethane adhesive;
the polyurethane adhesive is one of liquid polyurethane resin or two-liquid polyurethane resin;
the base cloth is one of non-woven fabric, woven fabric or superfine fiber synthetic leather base cloth.
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